N-oleoyl-2-ethylethylenimine



United States Patent 3,219,659 N-0LEOYL-Z-ETHYLETHYLENIMINE Evald L. Skau, Robert M. Mod, and Frank C. Magne, all of New (Brieans, La, assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. @riginal appiication Sept. 4-, 1964, Ser. No. 394,635. Divided and this application Apr. 13, 1965, Ser. No. 459,496

1 Claim. (Cl. 2613-239) (Granted under Title 35, U8. Code (1952), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to tie Government of the United States of America.

This application is a division of application Serial No. 394,636, filed September 4, 1964, which in turn is a continuation-in-part of application Serial No. 260,923, filed February 25, 1963.

This invention relates to certain compounds which are N-acyl derivatives of cyclic imines, to some unique mix tures of N-acyl derivatives of cyclic imines, and to plastic compositions, the plasticizer component of which is at least one of the compounds or one of the unique mixtures that are the subject of this invention. More particularly, this invention relates to N,N-disubstituted long chain aliphatic amides the acyl component of which is a normal, branched or substituted alkenoic or alkanoic acyl contain ing from 8 to 22 carbon atoms, the amide nitrogen in all cases being a member of a heterocyclic ring or in the case of a fused ring system one of the heterocyclic rings, all of the other ring members being carbon or nitrogen atoms.

This invention, in addition, relates to certain other new amide plasticizers wherein the acyl component is derived from dibasic alkanoic acids; epoxidized alkanoic, alkenoic, or alkandioic acids; dimer acids; cycloalkanoic, cycloalkenoic, cycloalkandioic, or cycloalkendioic acids which acids contain from 10-18 carbon atoms and in which acids the unsaturation if present may be in the cyclic group, the side chain, or both, such as the naphthenic, terpenederived, cyclized linoleic acids, and their epoxy derivatives.

This invention also relates to certain mixtures of the above-mentioned amides which individually or in combination wth other mxtures of amides are compatible plasticizers for vinyl chloride resins.

These compounds and the mixtures of these compounds are good, compatible, solvent-type plasticizers for polymers and copolymers of vinyl chloride resins. They are efiicient, primary, solvent-type plasticizers which can be made from low-price fatty acids. They impart excellent low-temperature properties, and good stability to northern-light exposure. Most important, they are characterized by their wide spectrum of anti-fungal and antimicrobial activity and When used alone or in admixtures with other plasticizers, impart these valuable properties to vinyl chloride plastics.

The terms vinyl type resin and vinyl chloride resin are used throughout this specification and claims to refer to polymers and copolymers of monomers containing vinyl chloride in a predominant proportion by weight. Terms such as compatible, good compatibility, and

3,2i9fi59 Patented Nov. 23, l$fi5 "ice compatible plasticizer in reference to the plasticizers which are the subject of this invention are used throughout the specification to refer to plasticizers that show no sign of exudation, migration to the surface, for at least two weeks when the plasticizers are present in the resin in proportions of about parts by weight of plasticizer to parts by weight of resin.

Not only are the compounds that are the subject of this invention useful as plasticizers for vinyl chloride resins, but they are also applicable as softeners for Buna N rubber.

If a resin is plasticized with a compound with which it has only limited compatibility, the plasticizer soon exudes or migrates to the surface unless the plasticizer is used either in a limited amount or is used in conjunc tion with a mutual solvent (a compatible auxiliary plasticizer) to obtain adequate compatibility.

It is known in the art that compounds similar to those which are the subject of this invention exhibit reasonably good compatibility for hydrophilic type resins but in order to obtain adequate flexibility must be employed together with a secondary or an auxiliary plasticizer as see for example United States Patent Number 2,339,056.

It would be expected from the recognized compatibility of compounds related to the type herein described with polyvinyl acetals (hydrophilic type resins), that these compounds would be quite incompatible with polymers of the vinyl chloride type. We have discovered, however, that not only are the particular compounds and compound mixtures herein described compatible as primary plasticizers with vinyl chloride resins but as we note above they are compatible with the hydrophilic type resins as well.

Not only are the particular compounds and mixtures of compounds herein described compatible vinyl type resin plasticizers, but the instant invention is considerably broader in that it also contemplates the use of the compatible (compatible with respect to the particular resin involved) binary, ternary, or multiple component mixtures of N-acyl cyclic imines of mixed saturated, monounsaturated, and polyunsaturated acids such as can be derived from animal, fish, or vegetable fats and oils such as tallows, white greases, menhaden oil, cottonseed oil, soybean oil, rapeseed oil, Crambe abyssznica seed oil, cuphea seed oil, jojobe oil, parsley seed oil, Limnanzlzea douglasii seed oil, palm oil, Vernom'a anthelmintz'ca seed oil, castor oil, foots, or from tall oil acids or rosin acids, and other seed oils.

The N-acyl derivatives of this invention decrease in their degree of compatibility as the alkyl portion of the acyl group (if saturated) increases in chain length beyond 15 carbon atoms and they are incompatible when the chain length is 17 or more carbon atoms. In general, the compatibility of a mixture of N-acyl cyclic imines containing a considerable proportion of these less compatible or incompatible N-acyl cyclic imines can be improved by mixing with a compatible plasticizer or by reducing the proportion of the incompatible saturated constituent by such procedures as fractional distillation or fractional crystallization either before or after the amidation step in the preparation of the N-acyl cyclic imine mixture. Similarly, the N-acyl derivatives of this invention decrease in their degree of compatibility as the alkyl portion of the acyl group of the N-acyl derivative (if unsaturated) in creases in unsaturation beyond monounsaturation. In

general, the compatibility of such a polyunsaturated derivative or of a mixture of N-acyl cyclic imines containing such polyunsaturated acyls can be increased by mixing With a suitable amount of a compatible plasticizer or by decreasing the polyunsaturation of some or all of the polyunsaturated constituents either by physical means, such as fractionation, or by chemical means such as selective hydrogenation, cyanoethylation, halogenation, epoxidation, formylation, maleination, dimerization, cyclization, or the like either before or after the amidation step in the preparation of the N-acyl imine or N-(mixed acyl) cyclic imine. The specific component ratio of compatible compositions can be established according to the scheme set forth in our copending application Serial No. 166,742, filed January 15, 1962. For example, all mixtures of the piperidide of linoleic acid (PL), i.e., N-linoleoylpiperidine, the piperidide of oleic acid (PO), and the piperidide of palmitic acid (PP), in which the weight fraction of PL is less than 35% are compatible plasticizers, the more important plasticizing characteristics of Which can be predicted approximately from those of the individual piperidides and their weight proportions in the given mixture.

Also included among the operable N-acyl cyclic imines are those whose acyls are acyls such as the acyls of the following types of acids: mono'basic and dibasic normal or branched chain alkanoic acids with substituents in the chain such as dichlorostearic acid; monoor dihydroxystearic acids; .acyloxyacids such as 12-acetoxyoleic, 12- acetoxystearic, 9,10-diacetoxystearic, acylated ricinoleic, a-oleoyloxypropionic acid, and the like; 12-beta cyanoethoxyoleic and 12-cyanoethoxystearic acids and the like; ricinoleic acid; phenylstear-ic acid; phenoxystearic acid; mono-, di-, or tri-epoxy stearic acids; monoor diepoxy oleic acid; epoxydocosanoic acid; dimerized or trimerized linolenic, linoleic, or oleic acid, etc.; cyclic acids such as cyclized linoleic and/or linolenic acids; Diels-Alder adducts of such polyenoic acids as tung oil acids or soybean acids; the Diels-Alder adducts of tung oil acids with dialkyl maleates, alkyl acrylates, acrylonitrile, fumaronitrile and the like; tall oil acids; rosin-derived or terpene-derived acids such as abietic, l-pimaric, pinonic, and the gammalactone of beta-hydroxyisopropyl pimelic acid; as well as the mono-alkyl esters of dibasic acids such as the monobutyl esters of pinic, adipic, sebacic, azelaic, brassylic, ca'rboxystearic, phthalic, and terephthalic acids, or of phosphonated fatty acids such as dialkyl phosphonostearic acid, and the like.

Also included among the operable N-acyl cyclic imines are the di-imides of di-basic acids, such as N,N'-sebacoyldipiperidine, in which the dibasic acid moiety may be that of pinic, adipic, sebacic, azelaic, brassylic, carboxystearic, phthalic and terephthalic acids, or the like.

Also included are the N,N'-diacyl cyclic di-irnines wherein the acylating groups are the acyl groups of the forementioned acids and wherein the acylating groups may be the same or different acyls; such as N,N'-didecanoylpiperazine, N-oleoyl-N'-acetylpiperazine or N- epoxyerucoyl-N'-butanoylpiperazine.

Also included are the N-acy1-N-a1kyl or N-acyl-N'- carbalkoxy cyclic di-imines wherein the acyl groups are the acyl groups of the forementioned acids and wherein the alkyl or carbalkoxy group contains from 111 carbon atoms; such as N-lauroyl-N'-methy1piperazine, N-epoxystearoyl N methylpiperazine, N-oleoyl-N'-carbethoxypiperazine or N-lauroyl-N-hexanoxycarbonylpiperazine. These are particularly effective as anti-microbial and antifungal agents.

Terms such as dimer acid, or dimerized acids are used indiscriminately to refer to acids or mixtures of acids consisting essentially of dibasic acids containing from 32 to 44 carbon atoms resulting from the polymerization or dimerization of long chain C to C unsaturated fatty acids. Terms such as trimer acid, or trime'rized acids are used indiscriminately to refer to acids or mixtures of acids consisting essentially of tribasic acids containing from 48 to 66 carbon atoms resulting from the polymerization or trimerization of long chain C to C unsaturated fatty acids.

Also included in this invention are the corresponding N-acyl derivatives of the alkanol and polyalkanol cyclic imines wherein the alkanol group or alkanol groups are acylated by the same acyl group as, or by .a different acyl group from, that acylating the imino nitrogen or wherein the alkanol group or alkanol groups are acylated by acyls containing from 2 to 6 carbon atoms; or wherein the alkanol group or alkanol groups are etherified with an alkyl group containing from 1 to 8 carbon atoms; exemplified by such compounds as N-oleoyl-4-(2-oleoyloxyethyl piperidine, N-decanoyl-4- (omega decanoyloxyalky1)piperidine, N-oleoyl 4-(3-butanoyloxypropy1) piperidine, N-butanoyl-4-(3-oleoyloxypropyl)piperidine, N-oleoyl-4-(2-ethoxyethy1)piperidine, and N-epoxystearoyl-4- (Z-butoxyethyl)piperi-dine and the like.

Also included among the operable N-acyl derivatives of this invention are the acyl derivatives of 3- to 7-membered substituted cyclic imines in which the substituents may include alkyl, aralkyl, aryl, hydroxy, acyloxy, .alkoxyalkyl, cyano, cyanoalkyl, alkoxy, ester, or carbalkoxy groups or the like.

The compounds of the instant invention were tested in vinyl chloride-vinyl acetate (-5) cop-olymer resin (Vinylite VYDR) and in polyvinylchloride (Geon 101) in a standard formulation comprising: 63.5% of Vinylite VYDR or Geon 101, 35% plasticizer, 0.5% stearic acid, and 1.0% basic lead carbonate. This formulation for each sample was milled, molded, and tested. In all examples, the sample was rated as incompatible if the molded stock showed any evidence of exudation or migration to the surface during a shelf storage of two weeks.

The compounds that are the subject of this invention are conveniently prepared by reacting the appropriate imine, which in every case is a cyclic imine wherein the nitrogen atom is a member of either the ring or a member of one of the rings if a fused ring compound is involved, With the appropriate acid, acid chloride, or ester. In any event, methods for preparing compounds such as those herein described are well known to those skilled in the art of fatty acid chemistry. The details of individual preparations are listed in the operating examples which follow:

Example 1 N-oleoylpiper-idine.-Twenty-two and four tenth grams (0.26 mole) of piperidine were dissolved in 60 milliliters of benzene and 39.7 grams (0.13 mole) of oleoyl chloride were added dropwise with stirring. After stirring for an additional hour, the reaction mixture was filtered, washed successively with dilute hydrochloric acid and water, and dried over anhydrous sodium sulfate. Free acid was removed by percolating the benzene solution through a column of activated alumina and eluting the amide with a 1:1 ethanol-benzene mixture. The solvent was then removed by stripping under reduced pressure. Analysis of the product, N-oleoylpiperidine; percent 0, 78.15 (theory 78.95); percent H, 12,07 (theory 12.40); percent N, 4.04 (theory 4.04).

Examiple 2 N-oleoylhxeamethylenimine. N oleoylhexamethylenimine was prepared by the procedure of Example 1 from 9.9 grams (0.10 mole) of hexamethylenimine, 30.0 grams (0.10 mole) of oleoyl chloride, and 8 grams (0.10 mole) of pyridine. Analysis of the product, N-oleoylhexamethylenimine: percent C, 78.83 (theory 79.21); percent H, 12.11 (theory 12.46); percent N, 3.79 (theory 3.85).

Example 3 N-oleoyI-Z-methylpiperi ine.A mixture of 31.6 grams (0.32 mole) of Z-methylpiperidine, 60 grams (0.21 mole) of oleic acid, and 20 milliliters of benzene was refluxed in an apparatus equipped with a Dean-Stark trap until the evolution of water ceased. The reaction mixture was diluted with 150 milliliters of commercial hexane, Washed successively with dilute hydrochloric acid and water, and dried over anhydrous sodium sulfate. Free acid was removed by percolating the hexane solution through a column of activated alumina, and eluting the amide with a 1:1 hexane-ethanol mixture. The solvent was removed by stripping under reduced pressure. Analysis of the product, N-oleoyl-Z-methylpiperidine: percent C, 78.87 (theory 79.20); percent H, 12.13 (theory 12.47); percent N, 3.86 (theory 3.85).

Example 4 N-oleoyl-3-methylpiperidine.-N-oleoyl-3-methylpiperidine was prepared by the procedure of Example 3 from 31.6 grams (0.32 mole) of 3-methylpiperidine, and 60 grams (0.21 mole) of oleic acid. Analysis of the product, N-oleoyl-3-methylpiperidine: percent C, 79.03 (theory 79.20); percent H, 12.30 (theory 12.47); percent N, 3.89 (theory 3.85).

Example 5 N-0le0yl-4-rrtethylpiperfdine.N-oleoyl-4-rnethylpiperidine was prepared by the procedure of Example 3 from 31.6 grams (0.32 mole) of 4-methylpiperidine and 60 grams (0.21 mole) of oleic acid. Analysis of the product, N-oleoyl-4-methylpiperidine: percent C, 78.80 (theory 79.20); percent H, 12.08 (theory 12.47); percent N, 3.86 (theory 3.85).

Example 6 N-oleoyl-4-ethylpiperidine. N oleoyl-4-ethylpiperidine was prepared by the procedure of Example 3 from 14.4 grams 0.13 mole) of 4-ethylpiperidine and 30 grams (0.11 mole) of oleic acid. Analysis of the product, N- oleoyl-4-ethylpiperidine: percent C, 79.17 (theory 79.45); percent H, 12.62 (theory 12.45); percent N, 3.75 (theory 371).

Example 7 N-oleoyl-4-nonylpiperidine.-N-oleoyl 4 nonylpiperidine was prepared by the procedure of Example 3 from 27 grams (0.13 mole) of 4-nonylpipen'dine and 30 grams (0.11 mole) of oleic acid. Analysis of the product, N- oleoyl-4-nonylpiperidine: percent C, 80.21 (theory 80.70); percent H, 12.67 (theory 12.80); percent N, 2.95 (theory 2.90).

Example 8 N-oleoyl-2methyI-S-ethylpiperidine. N oleoyl 2- methyl-S-ethylpiperidine was prepared from 27 grams (0.21 mole) of 2-methyl-S-ethylpiperidine and 40 grams (0.14 mole) of oleic acid by Example 3, except that toluene was used as the entraining solvent. Analysis of the product, N-oleoyl-2-methyI-S-ethylpiperidine: percent C, 79.51 (theory 79.66); percent H, 12.40 (theory 12.51); percent N, 3.79 (theory 3.85).

Example 9 Piperz'dide of selectively hydrogenated cottonseed oil fatty acids.The piperidide of selectively hydrogenated cottonseed oil fatty acids were prepared by the procedure of Example 3 from 18.6 grams (0.22 mole) of piperidine and 40 grams (0.14 mole) of selectively hydrogenated cottonseed oil fatty acids. (The selectively hydrogenated cottonseed oil fatty acids had an iodine value of 73.2, a thiocyanogen value of 68.0, and a neutralization equivalent of 274). The product, the piperidides of selectively hydrogenated cottonseed oil fatty acids, had a nitrogen content of 4.08%

Example 10 Piperidz'de of animal acids-The piperidide of animal acids (Neofat No. 65) was prepared by the procedure of Example 3 from 18.6 grams (0.22 mole) of piperidine and 40 grams (0.15 mole) of Neofat 65. (The animal acids consisted of a mixture of fatty acids having the following composition: 2% myristic, 26% palrnitic, 16% stearic, 48% oleic, and 8% linoleic acids). The product, the piperidide of animal acids, had a nitrogen content of 3.95%.

Example 11 N-0le0yIpyrr0lidz'ne.N oleoylpyrrolidine was prepared by the procedure of Example 3 from 15.1 grams (0.21 mole) of pyrrolidine and 40 grams (0.14 mole) of oleic acid. Analysis of the product, N-oleoylpyrrolidine: percent C, 77.81 (theory 78.67); percent H, 12.11 (theory 12.32); percent N, 4.30 (theory 4.17).

Example 12 N-oleoylJ,2,3,4-retrahydroquinoline. N-oleoyl-l,2, 3,4-tetrahydroquinoline was prepared from 15 grams (0.11 mole) of 1,2,3,4-tetrahydroquinoline, 35 grams (0.11 mole) of oleoyl chloride, and 9.2 grams (0.11 mole) of pyridine by the procedure of Example 1, except that the tree unreacted acid was removed by washing with 4% alcohol KOH followed by water washings. Analysis of the product N-oleoyl-1,2,3,4-tetrahydroquinoline: percent C, 80.89 (theory 81.48); percent H, 10.91 (theory 10.81); percent N, 3.31 (theory 3.52).

Example 13 N-oleoyl-2,6-dimethylpiperidine.N-oleoyl 2,6 dimethylpiperidine was prepared by the procedure of Example 1 from 30.1 grams (0.27 mole) of 2,6-dimethylpiperidine, and 40 grams (0.13 mole) of oleoyl chloride. Analysis of the product, N-oleoyl-2,6-dimethylpiperidine: percent C, 79.19 (theory 79.12); percent H, 12.43 (theory 12.30); percent N, 3.74 (theory 3.72).

Example 14 N-0le0ylcarbaz0le.-A mixture of 16.7 grams (0.10 mole) of carbazole, 30 grams (0.10 mole) of oleoyl chloride and 30 milliliters of xylene was refluxed for 4 hours. The reaction mixture Was Washed successively with dilute hydrochloric acid and water and dried over anhydrous sodium sulfate. Free acid was removed by percolating the xylene solution through a column of activated alumina and eluting the amide with a 1:1 ethanol-xylene mixture. The solvent was then removed by stripping under reduced pressure. Analysis of the product, N-oleoylcarbazole: percent C, 82.98 (theory 83.40); percent H, 9.50 (theory 9.50); percent N, 3.24 (theory 3.25).

Example 15 N-oleoyl-3-azabicyclo[3.2.2]nona.ne was prepared by the procedure of Example 12 from 12.5 grams (0.10 mole) of 3-azabicyclo[3.2.2]nonane, 30 grams (0.10 mole) of oleoyl chloride, and 8 grams (0.10 mole) of pyridine. Analysis of the product, n-oleoyl-3-azabicyclo[3.2.2]nonane: percent C, 79.20 (theory 80.09); percegt H, 11.95 (theory 12.06); percent N, 3.40 (theory 3. 0).

Example 16 N palmit0ylpiperidine.-N -.palrnitoylpipericline Was prepared by the procedure of Example 3 from 19 grams (0.22 mole) of piperidine and 40 grams (0.15 mole) of palmitic acid. Analysis of the product, N-palmitoylpiperidine: percent C, 78.02 (theory 77.88); percent H, 12.70 (theory 12.77); percent N, 3.89 (theory 4.33).

Example 1 7 N,N-sebac0yldipiperidine.-N,N' sebacoyldi-piperidine Was prepared by the procedure of Example 3 from 78 grams (0.92 mole) of piperidine and 40 grams (0.20 mole) of sebacic acid, except that the free unreacted acid was removed by dissolving the reaction product in carbon tetrachloride, treating with a slight excess of 4% alcoholic KOH, and washing with Water. Analysis of the product, N,N-sebacoyldipiperidine: percent C, 71.35 (theory 7 71.31); percent H, 10.63 (theory 10.70); percent N 8.18 (theory 8.32).

Example 18 N-stearoylpiperidine.N-stearoylpiperidine was prepared by the procedure of Example 3 from 27 grams (0.32 mole) of piperidine and 45 grams (0.16 mole) of stearic acid. Analysis of the product, N-stear-oylpiperidine: percent C, 78.50 (theory 78.49); percent H, 12.75 (theory 12.90); percent N, 3.96 (theory 3.98).

Example 19 Piperidide of dimer acid (Empol 1014).The piperidide of dimer acid was prepared by the procedure of Example 3 from 18.3 grams (0.22 mole) of piperidine and 40 grams (0.07 mole) of dimer acid (Empol 14). The product, the piperidide of dimer acid, had a nitrogen content of 3.98%.

Example 20 Mixed piperidides of oleic acid.This was a physical mixture consisting of 3.6% by weight of the sample of Example 3, 46.4% by weight of the sample of Example 4, 35.7% by weight of the sample of Example 5, and 14. 3% of the sample of Example 13.

Example 21 N-erucoylpiperidine.N-erucoylpiperidine was prepared by the procedure of Example 3 from 11.1 grams (0.13 mole) of piperidine and 40 grams (0.12 mole) of erucic acid. Analysis of the product, N-erucoylpiperidine: percent C, 79.84 (theory 79.86); percent H, 12.61 (theory 12.67); percent N, 3.48 (theory 3.41).

Example 22 N-decan0yl-4-n0nylpiperidine.N-decanoyl 4 nonylpiperidine was prepared by the procedure of Example 3 from 53 grams (0.25 mole) of 4-nonylpiperidine and 40 grams (0.23 mole) of decanoic acid. Analysis of the product, N-decanoyl-4-nonylpiperidine: percent C, 78.69 (theory 78.78); percent H, 12.90 (theory 12.96); percent N, 3.76 (theory 3.83).

Example 23 N-epoxystearoylpiperidine.N-epoxystearoylpiperidine was prepared by epoxidation of N-oleoylpiperidine using perbenzoic acid. The product, N-epoxystearoylpiperidine had an oxirane oxygen content of 4.49%.

Example 24 Piperz'dide of rapeseed oil fatty acids.The piperidide of rapeseed oil fatty acids was prepared by the procedure of Example 3 from 18.5 grams (0.22 mole) of piperidine and 60 grams (0.20 mole) of rapeseed oil fatty acids, the products, the piperidide of rapeseed oil fatty acids, had a nitrogen content of 3.56%.

Example 25 N,N'-diole0yl-dipiperidino methane.N,N' dioleoyl-dipiperidinomethane was prepared by the procedure of Example 3 from 18.1 grams (0.10 mole) of dipiperidinomethane and 50 grams (0.18 mole) of oleic acid. Analysis of the product, N,N'-dioleoyl-dipiperidinomethane:

' percent C, 78.52 (theory 79.30); percent H, 12.14 (theory 12.19); percent N, 3.94 (theory 3.94).

Example 26 8 Example 27 Mixed piperididea of oleic acid.-Mixed piperididea of oleic acid was prepared by the procedure of Example 31 from 55 grams (0.42 mole) of mixed piperidines (cornmercial by-product mixture of alkyl piperidines) and .100 grams (0.35 mole) of oleic acid. The product, the mixed piperidides of oleic acid, had a nitrogen content of 3.63%

Example 28 N,N'-di0le0ylpiperazine.N,N'-dioleoylpiperazine was prepared by the procedure of Example 3 from 9.2 grams (0.11 mole) of piperazine and 60 grams (0.2 1 mole) of oleic acid. Analysis of the product, N,N'-dioleoylpiperazine: percent C, 77.77 (theory 78.04); percent H, 12.12 (theory 12.13); percent N, 4.64 (theory 4.55).

Example 29 N-oleyl-N'-methyIpiperazine.-N-oleoyl N methylpiperazine was prepared by the procedure of Example 1 from 23.3 grams (0. 23 mole) of N-methylpiperazine and 35.0 grams (0.12 mole) of oleoyl chloride. Analysis of the product, N-oleoyl-N'-methylpiperazine: percent C, 74.46 (theory 75.70); percent H, 11.63 (theory 12.07); percent N, 7.43 (theory 7.68).

Example 30 N,N'-didecan0ylpiperazine.N,N' didecanoylpipera- Zine was prepared by the procedure of Example 17 from 13.8 grams (0.16 mole) of piperazine and 6012 grams (0.35 mole) of decanoi-c acid. Analysis of the product, N,N'-didecanoylpiperazine: percent C, 73.15 (theory 73.09); percent H, 1 1.68 (theory 11.75); percent N, 7.07 (theory 7.09).

Example 31 Piperidide of cottonseed oil fatty acids.-The piperidine of cottonseedoil fatty acids was prepared by the procedure of Example 3 from 18.6 grams (0.22 mole) of piperidine and 40 grams (0.1 4 mole) of cottonseed oil fatty acids. The product, the piperidide of cottonseed oil fatty acids, had a nitrogen content of 3.94%.

Example 32 N-linoleoylpiperidine.N-linoleoylpiperidine was prepared by the procedure of Example 3 from 20 grams (0.23 mole) of piperidine and 60 grams (0.21 mole) of linoleic acid. Analysis of the product, N-linoleoylpiperidine: percent C, 79.00 (theory 79.40); percent H, 11.77 (theory 11.89); percent N, 3.92 (theory 4.03).

The samples of Examples 1 to 36, inclusive, were evalu- .ated as plasticizers for Vinylite VYDR resin and the samples of Examples 1 and 16 were evaluated as plasticizers for Geon 101 using the afore-described formulations. The results are reported in Table 1 which includes the results for di-2-ethylhexylphthalate (DOP) as control.

The samples of Examples 1, 9; and 27 were evaluated as nitrile rubber (Hycar 1042-33% acrylonitrile) soften ers. The formulation employed was as follows:

Parts/ parts of rubber Percent Nitrile rubber (33% acrylonitrile) S R F black Zinc oxide Stearic acid. Sulfur Accelerator Softener TABLE I Tensile 100% Elonga- Brittle Volatility Compati- Example No. Plasticizer strength, modulus, tion, point, less, bility 8 psi. p.s.i. percent 0. percent N oleoylpiperidinm 2, 070 1, 170 390 C. N-oleoylpiperidine b 2, 990 1, 400 330 C. Noleoyliiexaniethylenimine 2, 650 1, 300 350 C. N-oleoyl-2-metl1ylpiperidine 2, 470 1, 240 310 39 0. 83 C. N-oleoyld-methylpiperidine 2, 500 1, 170 330 43 0. 79 O. N-oleoyll-methylpiperidine 1 2, 520 1, 240 310 43 0. 65 G. N oleoyl-4-ethylpiperidine 2, 760 1, 280 390 -45 0. 47 C. Nolcoyld ionylpiperidine 2, 780 l, 700 330 51 0. 27 C. N-oleoyl-2methyl-5-ethylpiperidiue 2, 870 1, 340 380 37 0. C. Piperidide oi hydrogenated cottonseed o 2, 660 1, 220 370 0.38 C. Piperidide of animal acids 0 2, 710 1, 180 370 39 0. 88 O. N-oleoylpyrrolidine 2, 400 990 370 C. N-oleoylJ,2,3,4tetrahydroquinoline 2, 990 1, 470 350 C. N -oleoyl-'2,fi-dimethylpiperidine 2, 990 1, 430 360 C. N-oleoylcarbazole 3, 500 2, 500 300 I. N -oleoyl-3-azabicyclo[3,2 1nonane 3, 000 l, 580 310 C. N -plamitoylpiperi line 2, 680 l, 160 350 C. N-plnmitoy piperidine b 2, 8*10 1, 300 350 C. N,N -sebacoyldipiper1dine 3, 040 1, 650 330 C. N-stearoylpiperidine 2, 770 1, 290 360 I. Piperidide o1 dimer acid (Empol 1014) 3,190 2, 630 180 0. Mixed piperidides of oleic acid d 2, 730 1, 290 350 C. N-erucoylpipeririine 2, 890 1, 380 400 C. Ndecanoyl--nonylpiperidinc 2, 880 1, 350 390 C. N -epoxystearoylpiperidine 2, 810 1, 180 340 C. Piperidide oi rapeseed oil fatty acids 2, 750 1,300 340 C. N,N dioleoyl-dipiperidinomethane 2, 840 1, 190 390 C. N oleoyl-4(5-nony1) piperidine 2, 990 1, 750 340 C. Mixed piperidides of oleic acid 6 2,910 1,380 37 C. N,N-dioleoylpipcrazine 2,800 1,330 380 I. N-oleoyl-N -rnet-hylpiperazine 2, 510 1, 810 280 I. N ,N dideeanoylpiperazine 2, 830 l, 770 250 I. Piperidide of cottonseed oil 1 y s. 2, 560 1, 200 330 C. N-linoleoylpiperidine- I, Piperidide of mixed acids C. Piperidide of mixed acids s C. Piperidide of mixed acids C. 36 Piperidide of mixed acids 1 C, Di 2-ethylhexylphthalate (control) 3, 050 1, 690 330 -33 1. 99 C O=Cornpatible, I=Incompatible.

b Using poly(vinyl chloride) homopolymcr instead of Vinylit-e V YD R resin.

v 2% myristie acid, 26% palmitic acid, 16% stearic acid, 48% oleic acid, and 8% linoleic acid.

Mixture of 3.6%, 46.4%, 35.7%, and 14.3% Examples 3, 4, 5, and 13, respectively.

= Made from a commercial byproduct mixture of alkyl pipericlines.

by weight of samples of Mixtm-e of 27.5%, 27.5%, and 45% by weight of the samples of Examples 1, 16, and 32, respectively.

TABLE II 300% Modulus, p.s.i. Tensile strength, p.s.i. Ultimate elongation,

percent Brittle Example No. Hardness, point, Volatility, Swelling,

Shore A C. percent percent Unnged Aged Unaged Aged Unaged Aged 600 990 1, 940 2, 140 710 510 48 0. 52 22. 2 5 50 1,000 1, 850 1, 950 700 510 52 -48 0. 96 22. 5 27 590 1, 050 1, 910 l, 930 680 500 53 -48 0. 94 22. 9 D38 (control) 960 1, 920 2, 170 2, 350 580 370 55 -55 5. 52 20. 9

Samples of Vinylite VYDR resin plasticizcd with the Noleoylpipcridine of Example 1, the N-oleoyl-Z-methylpiperidine of Example 3, the mixed piperidides of oleic acid of Example 20, and the N-oleoyl-2,6-dimcthylpiperidine of Example 13 respectively, were subjected to standard soil-burial tests using similar samples of VYDR resin plasticized with N-olcoylmorpholinc as controls. After 29 days localized areas of discoloration indicating microbial attack appeared in the control. None of the other specimens showed any signs of discoloration after 56 days. After 85 days the samples plasticized with N-oleoylpiperidine, and N-oleoyl-2-methylpipcridine were completely discolored, the sample plasticized with the mixed pipcridides of oleic acid showed only localized discoloration, and the sample plasticizcd with N-oleoyl-Z,6-dimcthylpiperidinc showed no signs of discoloration.

Improved light stability and thermal stability can be attained by inclusion of suitable stabilizers and/or antioxidants in the resin-plasticizer formulation.

The soapy water extractability can be reduced by the use of additives such as hydrocarbon extenders.

Example 37 N-aecanoyl-Z-metlzylpiperidine-l0.4 grams (0.10 mole) of Z-methylpiperidine were dissolved in 60 ml. of benzene and 10 grams (0.05 mole) of decanoy-l chloride Example 38 N decanoyl 3 methylpiperidine.-N decanoyl 3 methylpipen'dine was prepared by the procedure of EX- ample 37 from 11.9 grams (0.12 mole) of 3-methylpiperidine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-3-methylpiperidine: percent C, 75.01 (theory 75.78); percent H, 11.93 (theory 12.31); percent N, 5.39 (theory 5.52).

Example 39 N decanoyl 4 methylpiperidine.-N decanoyl 4 methylpiperidine was prepared by the procedure of Example 37 from 11.9 grams (0.12 mole) of 4-methylpiperidine and 10 grams (0.05 mole) of decanoyl chlo- 11 ride. Analysis of the product, N-decanoyl-4-methylpiperidine: percent C, 75.35 (theory 75.78); percent H, 12.20 (theory 12.31); percent N, 5.42 (theory 5.52).

Example 40 N decanoyl 4 ethylpiperidine.N decanoyl 4- ethylpiperidine was prepared by the procedure of Example 37 from 5.9 grams (0.05 mole) of 4-ethylpiperidine, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyll-et-hylpiperidine: percent C, 75.69 (theory 76.29); percent .H, 12.8 (theory 12.44); percent N, 5.10 (theory 5.24).

Example 41 N decanoyl-2-propylpiperidine.N-decanoyl-2-propylpiperidine was prepared by the procedure of Example 37 from 6.7 grams (0.05 mole) of 2-propylpiperidine, 4.2 'grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-2-propylpiperidine: percent C, 76.57 (theory 76.78); percent H, 12.50 (theory 12.54); percent N, 4.82 (theory 4.98).

Example 42 N-Decanyl-4-propylpiperidine.-N-decanoyl-4-propylpiperidine was prepared by the procedure of Example 37 from 6.7 grams (0.05 mole) of 4-propylpiperidine, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-4-propy1piperidine: percent C, 76.35 (theory 7678); percent H, 12.50 (theory 12.54); percent N, 4.82 (theory 4.98

Example 43 N -decan0yl-2- -n0nyl pi peridz'ne.N-decanoyl 2- 5 nonyl)piperidine was prepared by the procedure of Example 37 from 11.1 grams (0.05 mole) of 2-(5-nonyl) piperidine, 4.2 grams (0.05 mole) of pyridine and grams (0.05 mole) of decanoyl chloride. Analysis of the product, Ndecanoy1-2-(5-nonyl)piperidine: percent C, 78.59 (theory 78.78); percent H, 12.70 (theory 12.96); percent N, 3.7.5 (theory 3.83).

Example 44 N-decanoyl 2,6-dimethylpiperidine.N-decanoyl-2,6- dimethylpiperidine was prepared by the procedure of Example 37 from 5.94 grams (0.05 mole) of 2,6-dimethylpiperidine, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-2,6-dimethylpiperidine: percent C, 75.95 (theory 76.29); percent H, 12.38 (theory 12.44); percent N, 5.14 (theory 5.24).

Example 45 N-decanoyl-Z-methyl-S-ethylpiperidine.-N-decanoyl-2- methyl-S-ethylpiperidine was prepared by the procedure of Example 37 from 13.4 grams (0.10 mole) of Z-methyl- 5-ethylpiperidine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-2-methyl- S-ethylpiperidine: percent C, 76.49 (theory 76.81); percent H, 12.59 (theory 12.55); percent N, 4.98 (theory 4.98).

Example 46 N-decanoyl-Z-benzylpiperidine.-N-decanoyl-2-benzy1- piperidine was prepared by the procedure of Example 37 from 9.2 grams (0.05 mole) of 2-benzylpiperidine, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoyl chloride. Analysis of the product, N-decanoyl-2-benzylpiperidine: percent C, 80.13 (theory 80.19); percent H, 10.73 (theory 10.72); percent N, 4.16 (theory 4.26).

Example 47 N-decanoyl-4-benzylpiperidine.N-decanoyl-4-benzylpiperidine was prepared by the procedure of Example 37 from 9.2 grams (0.05 mole) of 4-benzylpiperidine, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) 12 of decanoyl chloride. Analysis of the product, N-decanoyl-4-benzylpiperidine: percent C, 80.37 (theory 80.19); percent H, 10.77 (theory 10.72); percent N, 4.20 (theory 4.26).

Example 48 N -decan0yl 3 -azabi1cy cl 0 [3 .2 .2 n0mme.N-decanoyl- 3-aza-bicyclo [3.2.2]nonane was prepared by the procedure of Example 37 from 6.6 grams (0.05 mole) of 3-azabicyclo[3.2.2]nonane, 4.2 grams (0.05 mole) of pyridine and 10 grams (0.05 mole) of decanoylchloride. Analysis of the product, N-decanoyl-3 aza bicyclo [3.2.2] nonane: percent C, 72.82 (theory 77.32); percent H, 10.95 (theory 11.81); percent N, 4.89 (theory 5.02).

Example 49 N-oleoyl-N'-car bethoxypiperazine-N-oleoyl-N'-carbethoxypiperazine was prepared by the procedure of Example 37 from 18.4 grams (0.12 mole) of ethyl N-piperazinocarboxylate, 9.2 grams (0.12 mole) of pyridine and 35 grams (0.12 mole) of oleoyl chloride. Analysis of the product, N-oleoyl-4-carbethoxypiperazine: percent C, 70.12 (theory 70.99); percent H, 10.85 (theory 10.88); percent N, 6.40 (theory 6.63

Example 50 N-(a-oleoyloxypropionyl)piperidine.l00 grams (1.17 mole) of piperidine and 69.4 grams (0.59 mole) of ethyl lactate was refluxed for 12 hours at a temperature just sufficient to liberate the ethanol formed. After the excess piperidine had been stripped under reduced pressure, the product N-lactoylpiperidine was obtained by vacuum distillation, solution in ether and percolation through a column of activated alumina. The solvent was then removed by stripping under reduced pressure. 27.5 grams (0.17 mole) of N-lactoylpiperidine and 13.9 grams (0.18 mole) of pyridine were dissolved in 100 ml. of benzene. Then 57.9 grams (0.19 mole) of oleoyl chloride were added dropwise with stirring. After stirring for an additional hour, the reaction mixture was filtered, washed successively with dilute hydrochloric acid and water, and dried over sodium sulfate. Free acid was removed by percolating the benezene solution through a column of activated alumina and eluting the amide with a 1:1 ethanol-benzene mixture. The solvent was removed by stripping under reduced pressure. Nitrogen content of the product, N-(a-oleoyloxypropionyl)piperidine, was 3.32 percent (theory 3.32).

Example 51 N-oleoyl Z-ethylethylenimine.N-oleoyl-2-ethylethylenimine was prepared by the procedure of Example 37 from 9.5 grams (0.13 mole) of 2-ethylethylenimine, 13.5 grams (0.13 mole) of triethylamine and 40 grams (0.13 mole) of oleoyl chloride. Nitrogen content of the product, N-01eoyl-2-ethylethylenimine, 3.93 percent (theory 4.17). This novel amide was not compatible as a pri mary plasticizer.

Example 52 The compounds of Examples 37 to 50, inclusive, were tested in vinyl chloride-vinyl acetate (-5) copolymer resin (Vinylite VYDR) in a standard formulation comprising: 63.5 percent of Vinylite VYDR, 35 percent plasticizer, 0.5 percent stearic acid, and 1.0 percent basic lead carbonate. This formulation for each sample was milled, molded, and tested. In these tests, the sample was rated as incompatible if the molded stock showed any evidence of exudation or migration to the surface during a shelf storage of two weeks.

Each of these novel products described in Examples 37 to 50, inclusive, proved to be compatible, primary plasticizers.

We claim:

N-oleoyl-2-ethylethylenimine.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner. 

